CN113272458A - Method for producing grain-oriented electromagnetic steel sheet - Google Patents

Method for producing grain-oriented electromagnetic steel sheet Download PDF

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Publication number
CN113272458A
CN113272458A CN202080008844.4A CN202080008844A CN113272458A CN 113272458 A CN113272458 A CN 113272458A CN 202080008844 A CN202080008844 A CN 202080008844A CN 113272458 A CN113272458 A CN 113272458A
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annealing
steel sheet
final
sheet
hot
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高谷真介
牛神义行
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • C21D10/00—Modifying the physical properties by methods other than heat treatment or deformation
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Abstract

The method for producing a grain-oriented electromagnetic steel sheet controls the degree of oxidation PH in the decarburization annealing step2O/PH2Controlling MgO and Al of the annealing separating agent in the annealing separating agent coating process2O3At the end of the mass ratio ofThe volume ratio of hydrogen in the mixed gas atmosphere is controlled to 50% or more in the annealing step, the solution to which the inhibitor is added is washed with water and then pickled in the annealing separator removing step, the mixed gas and temperature are controlled to perform annealing in the smoothing step, and the sintering temperature and heat treatment temperature are controlled in the insulating film forming step.

Description

Method for producing grain-oriented electromagnetic steel sheet
Technical Field
The present invention relates to a method for producing a grain-oriented electrical steel sheet.
The present application claims priority based on Japanese application No. 2019-005132 filed on 16.1.2019, the contents of which are incorporated herein by reference.
Background
Grain-oriented electrical steel sheets are mainly used in transformers. Since the transformer is continuously excited for a long time from the time of installation until the time of disposal, and energy loss continues to occur, the energy loss at the time of ac magnetization, that is, the iron loss, is a main index for determining the performance of the transformer.
In order to reduce the iron loss of grain-oriented electrical steel sheets, many methods have been proposed so far. For example, the steel sheet structure is a method for increasing the concentration in the {110} <001> orientation called a gaussian orientation, a method for increasing the content of solid solution elements such as Si for increasing the resistance, a method for reducing the thickness of the steel sheet, and the like.
Further, it is known that applying tension to a steel sheet is effective for reducing the iron loss. Therefore, a coating film is generally formed on the surface of the grain-oriented electrical steel sheet for the purpose of reducing the iron loss. The coating film reduces the iron loss of the steel sheet veneer by applying tension to the grain-oriented electrical steel sheet. When the grain-oriented electrical steel sheets are further stacked and used, the film reduces the iron loss of the core by ensuring the electrical insulation between the steel sheets.
As a grain-oriented electrical steel sheet on which a coating is formed, there is a steel sheet in which a forsterite coating, which is an oxide coating containing Mg, is formed on the surface of a mother steel sheet, and an insulating coating is further formed on the surface of the forsterite coating. That is, in this case, the coating on the mother steel sheet includes a forsterite coating and an insulating coating. The forsterite coating and the insulating coating each have two functions of an insulating function and a function of imparting tension to the mother steel sheet.
The forsterite film, which is an Mg-containing oxide film, is formed as follows: by the final annealing for generating the secondary recrystallization in the steel sheet, the annealing separating agent containing magnesium oxide (MgO) as the main component and the silicon oxide (SiO) formed on the mother steel sheet at the time of decarburization annealing2) The reaction is carried out at 900-1200 ℃ for more than 30 hours.
The insulating coating is formed by applying a coating solution containing phosphoric acid or phosphate, colloidal silica, and anhydrous chromic acid or chromate on the final-annealed mother steel sheet, and then baking and drying the coating solution at 300 to 950 ℃ for 10 seconds or more.
In order for the coating to exhibit functions of insulating properties and imparting tension to the mother steel sheet, high adhesion is required between the coating and the mother steel sheet.
Conventionally, the adhesion is mainly secured by an anchoring effect due to irregularities at the interface between the mother steel sheet and the forsterite film. However, in recent years, it has been clarified that the irregularities of the interface also become a factor of preventing the reduction of the iron loss because they become obstacles to the movement of the domain wall when the grain-oriented electrical steel sheet is magnetized.
In order to further reduce the iron loss, a technique for ensuring the adhesion of the insulating film in a state where the above-described interface is smoothed without a forsterite film which is an oxide film containing Mg is proposed in, for example, japanese patent laid-open No. s 49-096920 (patent document 1) and international publication No. 2002/088403 (patent document 2).
In the method for producing a grain-oriented electrical steel sheet disclosed in patent document 1, a forsterite coating is removed by pickling or the like, and the surface of a mother steel sheet is smoothed by chemical polishing or electrolytic polishing. In the method for producing a grain-oriented electrical steel sheet disclosed in patent document 2, alumina (Al) is used in the final annealing2O3) The annealing separator of (3) suppresses the formation of a forsterite film and smoothes the surface of the mother steel sheet.
However, in the manufacturing methods of patent documents 1 and 2, when the insulating coating is formed in contact with (directly on) the surface of the mother steel sheet, there is a problem that the insulating coating is difficult to adhere to (sufficient adhesion cannot be obtained) the surface of the mother steel sheet.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. S49-096920
Patent document 2: international publication No. 2002/088403
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above problems. The purpose of the present invention is to provide a method for producing a grain-oriented electrical steel sheet which does not have a forsterite coating film and is excellent in magnetic properties (particularly iron loss) and coating adhesion.
Means for solving the problems
The present inventors have studied a method for improving the adhesion (coating adhesion) between a steel sheet and an insulating coating on the premise that the insulating coating is formed on the surface of the steel sheet for grain-oriented electrical steel sheet having a smoothed steel sheet surface without forming a forsterite coating for reducing the iron loss.
As a result, they found that: by appropriately combining the predetermined steps, a grain-oriented electrical steel sheet having no forsterite coating and excellent magnetic properties and coating adhesion can be produced.
The gist of the present invention is as follows.
(1) A method for manufacturing a grain-oriented electrical steel sheet according to an aspect of the present invention includes:
a hot rolling step of obtaining a hot-rolled steel sheet by hot-rolling a steel slab having a chemical composition comprising, in mass%:
C：0.030～0.100％、
Si：0.80～7.00％、
Mn：0.01～1.00％、
total of S and Se: 0 to 0.060%,
Acid-soluble Al: 0.010-0.065%,
N：0.004～0.012％、
Cr：0～0.30％、
Cu：0～0.40％、
P：0～0.50％、
Sn：0～0.30％、
Sb：0～0.30％、
Ni：0～1.00％、
B：0～0.008％、
V：0～0.15％、
Nb：0～0.20％、
Mo：0～0.10％、
Ti：0～0.015％、
Bi：0～0.010％，
The remainder comprising Fe and impurities;
a cold rolling step of cold rolling the hot-rolled steel sheet to obtain a cold-rolled steel sheet;
a decarburization annealing step of performing decarburization annealing on the cold-rolled steel sheet to obtain a decarburization annealed sheet;
coating Al-containing decarburization annealing plate2O3An annealing separating agent coating step of drying the annealing separating agent and MgO;
a final annealing step of performing final annealing on the decarburized annealed sheet coated with the annealing separator to obtain a final annealed sheet;
an annealing separating agent removing step of removing the remaining annealing separating agent from the surface of the final annealed sheet;
a smoothing step of smoothing the surface of the final annealed sheet from which the excess annealing separator is removed; and
an insulating film forming step of forming an insulating film on the surface of the final annealed plate after the smoothing step,
in the above-mentioned decarburization annealing step,
at the oxidation degree, i.e. pH2O/PH2Is maintained at an annealing temperature of 750 to 900 ℃ for 10 to 600 seconds in an atmosphere of 0.18 to 0.80,
in the step of applying the annealing separator,
adding the annealing separating agentThe MgO and the Al2O3At a mass ratio of MgO/(MgO + Al)2O3) 5 to 50% and a hydration water content of 1.5 mass% or less,
in the above-mentioned final annealing process,
the decarburized and annealed sheet coated with the annealing separator is maintained at a temperature of 1100 to 1200 ℃ for 10 hours or more in a mixed gas atmosphere containing 50% or more by volume of hydrogen,
in the annealing separator removing step, the annealing separator is removed,
washing the final annealed plate with water using a solution containing an inhibitor of at least 1 of triethanolamine, rosin amine, or thiol,
pickling the final annealed plate with an acidic solution having a concentration of less than 20% by volume, whereby the amount of iron-based hydroxide and iron-based oxide on the surface of the final annealed plate is controlled to 0.9g/m per surface2In the following, the following description is given,
in the smoothing step, the smoothing step is carried out,
annealing the final annealed sheet from which the residual annealing separator has been removed at a temperature of 1000 ℃ or higher in a mixed gas atmosphere containing 50% or more by volume of hydrogen or carbon monoxide,
in the above-mentioned insulating coating film forming step,
and coating a coating liquid of an insulating film containing phosphate or colloidal silica as a main component on the surface of the smoothed final annealed plate, sintering the resultant at 350 to 600 ℃, and performing heat treatment at 800 to 1000 ℃ to form the insulating film.
(2) The method for producing a grain-oriented electrical steel sheet according to the above (1), wherein at least 1 of a hot-rolled sheet annealing step of annealing the hot-rolled steel sheet and a hot-rolled sheet pickling step of pickling may be provided between the hot-rolling step and the cold-rolling step.
(3) The method of producing a grain-oriented electrical steel sheet according to the item (1) or (2), wherein the decarburization annealing step may be performed by nitriding the cold-rolled steel sheet by annealing in an atmosphere containing ammonia.
(4) The method of manufacturing a grain-oriented electrical steel sheet according to any one of the above (1) to (3), wherein a magnetic domain control step of performing a magnetic domain control process may be provided between the cold rolling step and the decarburization annealing step, between the decarburization annealing step and the annealing separator application step, between the smoothing step and the insulating film forming step, or at any time after the insulating film forming step.
(5) The method for producing a grain-oriented electrical steel sheet according to any one of the above (1) to (4), wherein the steel slab may contain, in mass%, as a chemical composition, a chemical composition selected from the group consisting of:
Cr：0.02～0.30％、
Cu：0.05～0.40％、
P：0.005～0.50％、
Sn：0.02～0.30％、
Sb：0.01～0.30％、
Ni：0.01～1.00％、
B：0.0005～0.008％、
V：0.002～0.15％、
Nb：0.005～0.20％、
Mo：0.005～0.10％、
ti: 0.002 to 0.015% and
Bi：0.001～0.010％、
at least 1 of the group consisting.
Effects of the invention
According to the aspect of the present invention, it is possible to provide a method for producing a grain-oriented electrical steel sheet which does not have a forsterite film and is excellent in magnetic properties and film adhesion.
Drawings
Fig. 1 is a flowchart illustrating a method for manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the configuration disclosed in the present embodiment, and various modifications can be made without departing from the scope of the present invention. In addition, the numerical value limits shown in the present embodiment, and the lower limit value and the upper limit value are included in the range. Numerical values indicated as "above" or "below" are not included in the numerical range. The "%" of the content of each element means "% by mass" unless otherwise specified.
A method for producing a grain-oriented electrical steel sheet according to an embodiment of the present invention (hereinafter, sometimes referred to as a "method for producing a grain-oriented electrical steel sheet according to the present embodiment") is a method for producing a grain-oriented electrical steel sheet without a forsterite coating, and includes the following steps.
(i) Hot rolling step of hot rolling a billet having a predetermined chemical composition to obtain a hot-rolled steel sheet
(ii) A cold rolling step of subjecting the hot-rolled steel sheet to cold rolling once or twice or more with intermediate annealing interposed therebetween to obtain a cold-rolled steel sheet
(iii) A decarburization annealing step of subjecting the cold-rolled steel sheet to decarburization annealing to obtain a decarburization annealed sheet
(iv) Coating Al-containing decarburization annealing plate2O3And an annealing separator coating step of drying the annealing separator with MgO
(v) A final annealing step of subjecting the decarburized annealed sheet coated with the annealing separator to final annealing to obtain a final annealed sheet
(vi) An annealing separating agent removing step of removing the surplus annealing separating agent from the surface of the final annealed sheet by a method including water washing and acid washing
(vii) A smoothing step of smoothing the surface of the final annealed sheet from which the excess annealing separator is removed
(viii) An insulating film forming step of forming an insulating film on the surface of the final annealed plate after the smoothing
The method for producing a grain-oriented electrical steel sheet according to the present embodiment may further include the following steps.
(I) Annealing process of hot rolled sheet for annealing hot rolled sheet
(II) Hot rolled Steel plate Pickling step of Pickling Hot rolled Steel plate
(III) magnetic domain control step of performing magnetic domain control processing
The method of manufacturing a grain-oriented electrical steel sheet according to the present embodiment does not need to control only one of the above-described steps, and it is necessary to control the above-described steps in a composite and inseparable manner. By controlling all of the steps under predetermined conditions, the iron loss can be reduced and the film adhesion can be improved.
Hereinafter, each step will be described in detail.
< Hot Rolling Process >
In the hot rolling step, a composition containing, as a chemical composition, C: 0.030 to 0.100%, Si: 0.80 to 7.00%, Mn: 0.01 to 1.00%, the total of S + Se: 0 to 0.060%, acid-soluble Al: 0.010-0.065%, N: 0.004-0.012%, Cr: 0-0.30%, Cu: 0-0.40%, P: 0-0.50%, Sn: 0-0.30%, Sb: 0-0.30%, Ni: 0-1.00%, B: 0-0.008%, V: 0-0.15%, Nb: 0-0.20%, Mo: 0-0.10%, Ti: 0-0.015%, Bi: 0 to 0.010% and the balance of a billet containing Fe and impurities is hot-rolled to obtain a hot-rolled steel sheet. In the present embodiment, the steel sheet after the hot rolling step is referred to as a hot-rolled steel sheet.
The method of producing the billet (slab) to be subjected to the hot rolling step is not limited. For example, molten steel having a predetermined chemical composition may be melted and a slab may be manufactured using the molten steel. The slab may be produced by a continuous casting method, or a steel ingot may be produced using molten steel and the steel ingot may be cogging to produce a slab. Alternatively, the slab may be manufactured by another method.
The thickness of the slab is not particularly limited, and is, for example, 150 to 350 mm. The thickness of the slab is preferably 220-280 mm. As the slab, a so-called thin slab having a thickness of 10 to 70mm may be used.
First, the reasons for limiting the chemical composition of the billet will be described. Hereinafter,% of chemical composition means mass%.
[C：0.030～0.100％]
C (carbon) is an element effective for controlling the primary recrystallization structure, but is an element to be removed by decarburization annealing before the final annealing because it adversely affects the magnetic properties. If the C content of the billet exceeds 0.100%, the decarburization annealing time becomes long, and the productivity is lowered. Therefore, the C content is set to 0.100% or less. Preferably 0.085% or less, more preferably 0.070% or less.
The C content is preferably low, but the substantial lower limit of the C content is 0.030% in consideration of productivity in industrial production and magnetic properties of products.
[Si：0.80～7.00％]
Silicon (Si) increases the electrical resistance of grain-oriented electrical steel sheets and reduces the iron loss. If the Si content is less than 0.80%, a gamma-phase transformation occurs during the final annealing, and the crystal orientation of the grain-oriented electrical steel sheet is impaired. Therefore, the Si content is 0.80% or more. The Si content is preferably 2.00% or more, more preferably 2.50% or more. On the other hand, if the Si content exceeds 7.00%, cold workability is lowered, and cracks are likely to occur during cold rolling. Therefore, the Si content is 7.00% or less. The Si content is preferably 4.50% or less, and more preferably 4.00% or less.
[Mn：0.01～1.00％]
Manganese (Mn) increases the electrical resistance of grain-oriented electrical steel sheets to reduce the iron loss. Mn binds to S or Se to form MnS or MnSe, and functions as an inhibitor. When the Mn content is in the range of 0.01 to 1.00%, the secondary recrystallization is stable. Therefore, the Mn content is 0.01 to 1.00%. The lower limit of the Mn content is preferably 0.08%, and more preferably 0.09%. The upper limit of the Mn content is preferably 0.50%, and more preferably 0.20%.
[ total of either or both of S and Se: 0 to 0.060% ]
S (sulfur) and Se (selenium) are elements that combine with Mn to form MnS and/or MnSe that function as inhibitors.
If the total of either or both of S and Se (S + Se) exceeds 0.060%, the precipitation dispersion of MnS or MnSe becomes uneven after hot rolling. In this case, a desired secondary recrystallized structure cannot be obtained, the magnetic flux density is reduced, or MnS remains in the steel after purification, and the hysteresis loss is deteriorated. Therefore, the total content of S and Se is set to 0.060% or less.
The lower limit of the total content of S and Se is not particularly limited as long as it is 0%. The lower limit may be set to 0.003% or more. When used as an inhibitor, the content is preferably 0.015% or more.
Acid-soluble Al (sol. Al): 0.010-0.065% ]
Acid-soluble Al (aluminum) (sol. Al) is an element that bonds with N to produce AlN or (Al, Si) N that functions as an inhibitor. When the acid-soluble Al content is less than 0.010%, the effect is not sufficiently exhibited, and secondary recrystallization does not sufficiently proceed. Therefore, the acid-soluble Al content is set to 0.010% or more. The acid-soluble Al content is preferably 0.015% or more, and more preferably 0.020% or more.
On the other hand, if the acid-soluble Al content exceeds 0.065%, the precipitation dispersion of AlN, (Al, Si) N becomes non-uniform, a desired secondary recrystallized structure cannot be obtained, and the magnetic flux density decreases. Therefore, the acid-soluble Al (sol. Al) is set to 0.065% or less. The acid-soluble Al content is preferably 0.055% or less, and more preferably 0.050% or less.
[N：0.004～0.012％]
N (nitrogen) is an element that bonds with Al to form AlN, (Al, Si) N functioning as an inhibitor. If the N content is less than 0.004%, formation of AlN, (Al, Si) N becomes insufficient, so that N is set to 0.004% or more. Preferably 0.006% or more, more preferably 0.007% or more.
On the other hand, if the N content exceeds 0.012%, blisters (voids) may be formed in the steel sheet. Therefore, the N content is set to 0.012% or less.
The chemical composition of the billet contains the elements, and the balance contains Fe and impurities. However, considering the strengthening of the inhibitor function by the formation of the compound and the influence on the magnetic properties, 1 or 2 or more kinds of the selected elements may be contained in the following ranges instead of part of Fe. Examples of the optional element to be contained in place of part of Fe include Cr, Cu, P, Sn, Sb, Ni, B, V, Nb, Mo, Ti, and Bi. Since the selective element may not be contained, the lower limit thereof is 0%. Further, even if these optional elements are contained as impurities, the above effects are not impaired. The term "impurities" refers to substances mixed in from ores and scraps as raw materials or from a production environment or the like in the industrial production of steel.
[Cr：0～0.30％]
Cr (chromium) is an element effective for increasing the electric resistance and reducing the iron loss, similarly to Si. Therefore, Cr may be contained. In the case where the above effects are obtained, the Cr content is preferably 0.02% or more, and more preferably 0.05% or more.
On the other hand, if the Cr content exceeds 0.30%, the decrease in magnetic flux density becomes a problem, so the upper limit of the Cr content is preferably 0.30%, more preferably 0.20%, and still more preferably 0.12%.
[Cu：0～0.40％]
Cu (copper) is also an element effective for increasing the electric resistance and reducing the iron loss. Therefore, Cu may be contained. In the case where this effect is obtained, the Cu content is preferably 0.05% or more, and more preferably 0.10% or more.
On the other hand, if the Cu content exceeds 0.40%, the iron loss reduction effect may be saturated, and may cause surface defects of "copper scale folding" at the time of hot rolling. Therefore, the upper limit of the Cu content is preferably 0.40%, more preferably 0.30%, and still more preferably 0.20%.
[P：0～0.50％]
P (phosphorus) is also an element effective for increasing the resistance and reducing the iron loss. Therefore, P may be contained. In the case where this effect is obtained, the P content is preferably 0.005% or more, and more preferably 0.010% or more.
On the other hand, if the P content exceeds 0.50%, rolling property may be problematic. Therefore, the upper limit of the P content is preferably 0.50%, more preferably 0.20%, and still more preferably 0.15%.
[Sn：0～0.30％]
[Sb：0～0.30％]
Sn (tin) and Sb (antimony) are effective elements for stabilizing secondary recrystallization and developing the {110} <001> orientation. Therefore, Sn or Sb may be contained. In the case where this effect is obtained, the Sn content is preferably 0.02% or more, and more preferably 0.05% or more. The Sb content is preferably 0.01% or more, and more preferably 0.03% or more.
On the other hand, if Sn exceeds 0.30% or Sb exceeds 0.30%, the magnetic properties may be adversely affected. Therefore, the upper limits of the Sn content and the Sb content are preferably set to 0.30%. The upper limit of the Sn content is more preferably 0.15%, and still more preferably 0.10%. The upper limit of the Sb content is more preferably 0.15%, and still more preferably 0.10%.
[Ni：0～1.00％]
Ni (nickel) is also an element effective for increasing the electric resistance and reducing the iron loss. In addition, Ni is an element effective for improving the magnetic properties by controlling the metal structure of the hot-rolled steel sheet. Therefore, Ni may be contained. In the case where the above-described effects are obtained, the Ni content is preferably 0.01% or more, and more preferably 0.02% or more.
On the other hand, if the Ni content exceeds 1.00%, the secondary recrystallization may become unstable. Therefore, the Ni content is preferably set to 1.00% or less, more preferably 0.20% or less, and still more preferably 0.10% or less.
[B：0～0.008％]
B (boron) is an element effective for forming BN that exhibits an inhibitor effect by binding to N. Therefore, B may be contained. In the case where the above-described effects are obtained, the B content is preferably 0.0005% or more, more preferably 0.0010% or more.
On the other hand, if the B content exceeds 0.008%, the magnetic characteristics may be adversely affected. Therefore, the upper limit of the B content is preferably 0.008%, more preferably 0.005%, and further preferably 0.003%.
[V：0～0.15％]
[Nb：0～0.20％]
[Ti：0～0.015％]
V (vanadium), Nb (niobium), and Ti (titanium) are elements that function as inhibitors by binding to N, C. Therefore, V, Nb or Ti may be contained. In the case where the above-described effects are obtained, the V content is preferably 0.002% or more, and more preferably 0.010% or more. The Nb content is preferably 0.005% or more, and more preferably 0.020% or more. The Ti content is preferably 0.002% or more, more preferably 0.004% or more.
On the other hand, if the steel slab contains V in a range exceeding 0.15%, Nb in a range exceeding 0.20%, and Ti in a range exceeding 0.015%, these elements remain in the final product, and the V content exceeds 0.15%, the Nb content exceeds 0.20%, or the Ti content exceeds 0.015% may be present as the final product. In this case, the magnetic properties of the final product (electrical steel sheet) may be deteriorated.
Therefore, the upper limit of the V content is preferably 0.15%, more preferably 0.10%, and still more preferably 0.05%. The upper limit of the Ti content is preferably 0.015%, more preferably 0.010%, and still more preferably 0.008%. The upper limit of the Nb content is preferably 0.20%, more preferably 0.10%, and still more preferably 0.08%.
[Mo：0～0.10％]
Mo (molybdenum) is also an element effective for increasing the resistance and reducing the iron loss. Therefore, Mo may be contained. In the case where the above-described effects are obtained, the Mo content is preferably 0.005% or more, and more preferably 0.01% or more.
On the other hand, if the Mo content exceeds 0.10%, the rolling properties of the steel sheet may be problematic. Therefore, the upper limit of the Mo content is preferably 0.10%, more preferably 0.08%, and still more preferably 0.05%.
[Bi：0～0.010％]
Bi (bismuth) is an element effective for stabilizing precipitates such as sulfides and enhancing the function as an inhibitor. Therefore, Bi may be contained. In the case where the above-described effects are obtained, the Bi content is preferably 0.001% or more, and more preferably 0.002% or more.
On the other hand, if the Bi content exceeds 0.010%, the magnetic properties may be adversely affected. Therefore, the upper limit of the Bi content is preferably 0.010%, more preferably 0.008%, and further preferably 0.006%.
The chemical composition described above may be measured by a general analysis method of steel. For example, the chemical composition may be measured by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry). The sol.al may be measured by ICP-AES using a filtrate obtained by thermally decomposing a sample with an acid. C and S may be measured by a combustion-infrared absorption method, N may be measured by an inert gas melting-thermal conductivity method, and O may be measured by an inert gas melting-non-dispersive infrared absorption method.
Next, conditions for hot rolling the slab will be described.
The hot rolling conditions are not particularly limited. For example, the following conditions are used.
The slab is heated prior to hot rolling. The slab is charged into a known heating furnace or a known soaking furnace and heated. As 1 method, the slab was heated to 1280 ℃ or less. By setting the heating temperature of the slab to 1280 ℃ or lower, various problems (e.g., a special heating furnace is required, and the amount of molten oxide scale is large) when heating at a temperature higher than 1280 ℃ can be avoided. The lower limit of the heating temperature of the slab is not particularly limited. When the heating temperature is too low, hot rolling becomes difficult, and productivity may be lowered. Therefore, the heating temperature may be set in consideration of productivity within a range of 1280 ℃ or less. The preferred lower limit of the heating temperature of the slab is 1100 ℃. The preferred upper limit of the heating temperature of the slab is 1250 ℃.
As another method, the slab is heated to a high temperature of 1320 ℃. By heating to a high temperature of 1320 ℃ or higher, AlN and Mn (S, Se) are melted and finely precipitated in the subsequent step, and secondary recrystallization can be stably expressed.
The slab heating step itself may be omitted, and the hot rolling may be started after the casting before the temperature of the slab is lowered.
Next, hot rolling using a hot rolling mill is performed on the heated slab to manufacture a hot-rolled steel sheet. The hot rolling mill includes, for example, a roughing mill and a finishing mill disposed downstream of the roughing mill. The roughing mill is provided with roughing stands arranged in a row. Each roughing stand includes a plurality of rolls arranged one above the other. The finishing mill is similarly provided with finishing mill stands arranged in a row. Each finish rolling stand includes a plurality of rolls arranged in an up-down manner. The heated steel material is rolled by a roughing mill, and then further rolled by a finishing mill to produce a hot-rolled steel sheet.
The final temperature in the hot rolling step (the temperature of the steel sheet on the exit side of the finish rolling stand where the steel sheet is finally rolled down by the finish rolling mill) is, for example, 700 to 1150 ℃. The hot-rolled steel sheet is produced through the hot rolling step described above.
< annealing Process of Hot rolled sheet >
In the hot-rolled sheet annealing step, the hot-rolled steel sheet obtained in the hot-rolling step is annealed (hot-rolled sheet annealing) as necessary to obtain a hot-rolled annealed sheet. In the present embodiment, the steel sheet after the hot-rolled sheet annealing step is referred to as a hot-rolled annealed sheet.
The hot-rolled sheet annealing is performed for the purpose of making the uneven structure generated during hot rolling as uniform as possible, controlling the precipitation (fine precipitation) of AlN as an inhibitor, controlling the second phase/solid-solution carbon, and the like. The annealing conditions may be selected from known conditions according to the purpose. For example, when the uneven structure generated during hot rolling is made uniform, the hot-rolled steel sheet is held at an annealing temperature (furnace temperature in a hot-rolled sheet annealing furnace) of 750 to 1200 ℃ for 30 to 600 seconds.
The hot-rolled sheet annealing is not necessarily performed, and the presence or absence of the hot-rolled sheet annealing step may be determined depending on the characteristics and the production cost required for the grain-oriented electrical steel sheet to be finally manufactured.
< Hot rolled plate Pickling Process >
In the hot-rolled sheet pickling step, pickling is performed on the hot-rolled steel sheet after the hot-rolling step or, in the case of annealing the hot-rolled sheet, on the hot-rolled annealed sheet after the hot-rolled sheet annealing step, as necessary, in order to remove scale formed on the surface. The acid washing conditions are not particularly limited, and may be performed under known conditions.
< Cold Rolling Process >
In the cold rolling step, the hot-rolled steel sheet or the hot-rolled annealed sheet after the hot rolling step, after the hot-rolled sheet annealing step, or after the hot-rolled sheet pickling step is subjected to cold rolling once or twice or more with intermediate annealing interposed therebetween to produce a cold-rolled steel sheet. In the present embodiment, the steel sheet after the cold rolling step is referred to as a cold-rolled steel sheet.
The cold rolling reduction (the cumulative cold rolling reduction without intermediate annealing or the cumulative cold rolling reduction after intermediate annealing) in the final cold rolling is preferably 80% or more, and more preferably 90% or more. The upper limit of the final cold rolling reduction is preferably 95%.
Here, the final cold rolling reduction (%) is defined as follows.
Final cold rolling reduction (%) (1-thickness of steel sheet after final cold rolling/thickness of steel sheet before final cold rolling) × 100
< decarburization annealing step >
In the decarburization annealing step, the cold-rolled steel sheet produced in the cold rolling step is subjected to a magnetic domain control treatment as necessary, and thereafter subjected to decarburization annealing to be recrystallized once. In addition, C, which adversely affects the magnetic properties, is removed from the steel sheet in the decarburization annealing. In the present embodiment, the steel sheet after the decarburization annealing process is referred to as a decarburization annealed sheet.
For the above purpose, in the decarburization annealing, the oxidation degree (PH) is set2O/PH2) The temperature is maintained at an annealing temperature of 750 to 900 ℃ for 10 to 600 seconds in an atmosphere of 0.18 to 0.80. The degree of oxidation, namely pH2O/PH2Can be controlled by the partial pressure of water vapor PH in the atmosphere2O (atm) and hydrogen partial pressure PH2(atm) ratio.
If degree of oxidation (PH)2O/PH2) When the amount is less than 0.18, the external oxidation type dense silicon oxide (SiO) is rapidly formed2) The diffusion of carbon out of the system is hindered, thereby causing desorptionCarbon was poor. On the other hand, if it exceeds 0.80, the oxide film on the surface of the steel sheet becomes thick and removal becomes difficult.
Further, if the annealing temperature is less than 750 ℃, decarburization cannot be sufficiently performed. On the other hand, if it exceeds 900 ℃, the primary recrystallized grain size exceeds the desired size, and therefore the magnetic properties after the final annealing are deteriorated.
Further, if the holding time is less than 10 seconds, decarburization cannot be sufficiently performed. On the other hand, if it exceeds 600 seconds, the primary recrystallized grain size exceeds the desired size, and therefore the magnetic properties after the final annealing are deteriorated.
The oxidation degree (pH) may be determined in accordance with the above2O/PH2) The heating rate in the temperature raising process up to the annealing temperature is controlled. For example, when heating including induction heating is performed, the average heating rate may be set to 5 to 1000 ℃/sec. In addition, when heating including electric heating is performed, the average heating rate may be set to 5 to 3000 ℃/sec.
In the decarburization annealing step, the cold-rolled steel sheet may be further subjected to nitriding treatment by annealing in an atmosphere containing ammonia to nitride the cold-rolled steel sheet at any one or two or more stages before, during, or after the above-described holding. When the slab heating temperature is low, the decarburization annealing step preferably includes a nitrogen treatment. By further performing the nitriding treatment in the decarburization annealing step, inhibitors such as AlN, (Al, Si) N, etc. are generated, and therefore secondary recrystallization can be stably expressed.
The conditions for the nitriding treatment are not particularly limited, but the nitriding treatment is preferably performed so that the nitrogen content is increased by 0.003% or more, preferably by 0.005% or more, and more preferably by 0.007% or more. If the nitrogen (N) content is 0.030% or more, the effect is saturated, and therefore the nitriding treatment may be performed so as to be 0.030% or less.
The conditions for the nitriding treatment are not particularly limited, and may be performed under known conditions.
For example, oxidation at 0.01 to 0.15Degree (PH)2O/PH2) And, in the case of performing the nitriding treatment after holding the steel sheet at 750 to 900 ℃ for 10 to 600 seconds, the steel sheet is held in an ammonia-containing atmosphere during the cooling without cooling the steel sheet to room temperature. The degree of oxidation (pH) is preferably reduced during the cooling2O/PH2) Set to be in the range of 0.0001 to 0.01. At an oxidation degree (pH) of 0.01 to 0.152O/PH2) And, when the nitriding treatment is performed while maintaining the temperature at 750 to 900 ℃ for 10 to 600 seconds, ammonia may be introduced into the atmosphere gas having the oxidation degree.
< annealing separator application step >
In the annealing separating agent application step, the decarburization annealed sheet after the decarburization annealing step (including the decarburization annealed sheet after the nitriding treatment) is subjected to a magnetic domain control treatment as necessary, and then coated with an Al-containing coating film2O3And an annealing separator of MgO, and drying the applied annealing separator.
The annealing separating agent contains MgO and does not contain Al2O3In the case of (3), a forsterite coating is formed on the steel sheet in the final annealing step. On the other hand, the annealing separator contains Al2O3In the case of not containing MgO, mullite (3 Al) is formed in the steel sheet2O3·2SiO2). This mullite acts as an obstacle to the movement of a magnetic domain wall, and thus causes deterioration of the magnetic properties of the grain-oriented electrical steel sheet.
Therefore, in the method for producing a grain-oriented electrical steel sheet according to the present embodiment, an annealing separator containing Al is used2O3And an annealing separator of MgO. By using a catalyst containing Al2O3And an annealing separator of MgO, and can obtain a steel sheet having a smooth surface without forming a forsterite film on the surface after the final annealing.
In the annealing separating agent, MgO and Al are mixed2O3At a mass ratio of MgO/(MgO + Al)2O3) The content of hydrated water is set to 5 to 50% and the content of hydrated water is set to 1.5 mass% or less.
MgO/(MgO+Al2O3) Less than 5%When the amount of mullite is large, the iron loss is deteriorated. On the other hand, if it exceeds 50%, the iron loss is deteriorated due to the formation of forsterite.
Further, if the hydration moisture in the annealing separator exceeds 1.5 mass%, secondary recrystallization may become unstable or the surface of the steel sheet may be oxidized (to form SiO) in the final annealing2) The surface of the steel sheet becomes difficult to smooth. The lower limit of the hydration moisture is not particularly limited, and may be set to 0.1 mass%, for example.
The annealing separator is applied to the surface of the steel sheet by aqueous slurry coating, electrostatic coating, or the like. In the annealing separator application step, a nitride such as manganese nitride, iron nitride, or chromium nitride, which is decomposed before secondary recrystallization in the final annealing step and nitrided into a decarburized steel sheet or decarburized nitrided sheet, may be added to the annealing separator.
< Final annealing Process >
And finally annealing the decarburized annealed sheet coated with the annealing separating agent to prepare a final annealed sheet. The decarburized annealed sheet coated with the annealing separator is subjected to final annealing, and secondary recrystallization proceeds, whereby the crystal orientation is concentrated in the {110} <001> orientation. In the present embodiment, the steel sheet after the final annealing step is referred to as a final annealed sheet.
Specifically, in the final annealing step, the decarburized and annealed sheet coated with the annealing separator is held at a temperature of 1100 to 1200 ℃ for 10 hours or more in a mixed gas atmosphere containing 50% or more by volume of hydrogen. The upper limit of the annealing time is not particularly limited, and may be set to 30 hours, for example. By this finish annealing, the above-mentioned secondary recrystallization proceeds in the decarburization annealed slab, and the crystal orientation is concentrated in the {110} <001> orientation.
< annealing separator removal step >
In the annealing separator removing step, the excess annealing separator such as the unreacted annealing separator that has not reacted with the steel sheet in the final annealing is removed from the surface of the finally annealed steel sheet (final annealed sheet) by a method including water washing and acid washing.
Specifically, first, from the viewpoint of preventing corrosion of iron after removal by washing with water, the final annealed plate is washed with water using a solution to which at least 1 of triethanolamine, rosin amine, or mercaptan is added as an inhibitor (anticorrosive agent).
After the final annealed plate is washed with water, only an acid solution with a volume ratio concentration of less than 20% is used for acid washing. For example, the final annealed sheet is pickled with a solution containing 1 or 2 or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, chloric acid, chromium oxide aqueous solution, chromium sulfate, permanganic acid, peroxosulfuric acid, and peroxophosphoric acid in a total amount of less than 20 vol%. The lower limit of the volume-to-volume concentration is not particularly limited, and may be set to 0.1 vol%, for example. The volume% may be set to a ratio based on the volume at room temperature.
By performing water washing and acid washing using these solutions, the excess annealing separator remaining on the surface of the final annealed sheet can be effectively removed.
The liquid temperature of these solutions is preferably set to 20 to 80 ℃. By setting the liquid temperature in the above range, the excess annealing separator on the surface of the steel sheet can be effectively removed.
By the water washing and acid washing, the amount of iron-based hydroxide and iron-based oxide on the surface of the final annealed sheet were controlled to be 0.9g/m in total per one surface2The following.
Insufficient removal of the surplus annealing separator on the steel sheet surface, and the total amount of iron-based hydroxide and iron-based oxide on the steel sheet surface exceeding 0.9g/m per surface2In the case of (3), the exposure of the base metal surface is insufficient, and therefore there is a possibility that the subsequent smoothing of the steel sheet surface cannot be sufficiently performed. The lower limits of the amount of iron-based hydroxide and the amount of iron-based oxide are not particularly limited, and may be set to 0.01g/m2And (4) finishing.
In order to remove the excess annealing separator, a scrubber may be used in addition to the above-described water washing and acid washing. By using the washer, it is possible to reliably remove the excess annealing separator that deteriorates the wettability in the insulating film forming step.
< smoothing step >
After exposing the base metal by performing the above-described water washing and acid washing, the final annealed sheet having a smoothed surface (base metal surface) is obtained by annealing at a temperature of 1000 ℃ or higher in a mixed gas atmosphere containing hydrogen or carbon monoxide in a volume ratio of 50% or more. Hereinafter, annealing for smoothing is referred to as smoothing annealing.
In the smoothing annealing, the steel sheet having the base metal surface exposed is heated in a mixed gas atmosphere containing a reducing gas, thereby causing the atoms to evaporate and move from the base metal surface, and a smooth surface without magnetic pinning is formed. The gas to be mixed with the reducing gas is preferably an inert gas such as nitrogen or argon. The use of a mixed gas of hydrogen and nitrogen is the lowest cost in industry, but carbon monoxide can also be used as a substitute for hydrogen.
If the volume ratio of hydrogen or carbon monoxide contained in the mixed gas atmosphere in the smoothing annealing is less than 50%, the metallic luster decreases due to oxidation of the base metal surface, and as a result, the magnetic properties of the final product deteriorate. The smoothing effect of the base metal surface becomes large if the volume fraction of hydrogen or carbon monoxide is increased, but this effect is exhibited if the mixed gas atmosphere contains 50% or more of hydrogen or carbon monoxide by volume fraction, so the lower limit of the volume fraction of hydrogen or carbon monoxide is set to 50%. The upper limit of the volume ratio of hydrogen or carbon monoxide is not particularly limited, and may be set to 100%, for example.
When the annealing temperature in the smoothing annealing is high, the smoothing effect can be obtained in a short time, but if the annealing temperature is 1000 ℃ or more, the evaporation and movement of atoms from the surface of the base metal can be effectively promoted. Further, when the annealing temperature in the smoothing annealing is less than 1000 ℃, the smoothing effect becomes insufficient and the magnetic characteristics become poor. Therefore, the lower limit of the annealing temperature in the smoothing annealing is set to 1000 ℃. The upper limit of the annealing temperature in the smoothing annealing is not particularly limited, but if the annealing temperature exceeds 1200 ℃, the smoothing effect is saturated, so the annealing temperature is preferably controlled to 1200 ℃ or less.
In the case where the surface of the final annealed sheet has irregularities, the irregularities hinder the movement of the magnetic domain wall, and thus the iron loss increases. However, by performing the smoothing annealing described above after sufficiently exposing the surface of the final annealed sheet, a smooth state with extremely high flatness can be obtained, and a high iron loss improvement effect can be obtained by smoothly performing the movement of the magnetic domain wall.
< insulating coating Forming Process >
In the insulating film forming step, the surface of the final annealed plate after the smoothing is subjected to magnetic domain control processing as necessary, and then an insulating film is formed. In the present embodiment, the steel sheet after the insulating coating forming step is referred to as a grain-oriented electrical steel sheet.
The insulating coating film reduces the iron loss of the steel sheet veneer by applying tension to the grain-oriented electrical steel sheet, and reduces the iron loss of the iron core by ensuring electrical insulation between the steel sheets when the grain-oriented electrical steel sheet is laminated and used.
The insulating film is formed by applying a coating liquid of an insulating film containing at least one of phosphate and colloidal silica as a main component to the surface of the final annealed plate, sintering the resultant at 350 to 600 ℃, and then performing heat treatment at 800 to 1000 ℃.
The phosphate is preferably a phosphate of Ca, Al, Sr, or the like, and among them, an aluminum phosphate salt is more preferable. The colloidal silica is not particularly limited to colloidal silica of a specific nature. The particle size is also not particularly limited to a specific particle size, but is preferably 200nm or less (number average particle diameter). For example, 5 to 30 nm. If the particle size exceeds 200nm, there is a possibility of sedimentation in the coating liquid. Further, the coating liquid may further contain anhydrous chromic acid or chromate.
If the sintering temperature of the insulating film is less than 350 ℃, the insulating film causes a droplet flow in the through plate, which causes a poor appearance, and an insulating film having sufficient adhesion cannot be obtained. If the temperature exceeds 600 ℃, only the outermost surface of the insulating film is cured because the heating rate is too high, and the curing inside is delayed, which causes poor film formation and insufficient film adhesion. Further, if the heat treatment temperature after firing is less than 800 ℃, film formation is poor (hardening is insufficient), and sufficient film tension cannot be obtained. Further, if the temperature exceeds 1000 ℃, decomposition of phosphate occurs, resulting in poor film formation and insufficient film adhesion.
In the formation of the coating film, the oxidation degree (PH) of the atmosphere is adjusted2O/PH2) The amount is preferably 0.01 to 1.5, since the insulating film can be formed without decomposing the phosphate to a greater extent than necessary.
The coating liquid for forming an insulating coating film can be applied to the surface of the steel sheet by a wet coating method such as a roll coater, for example.
< magnetic domain control step >
In the method of manufacturing a grain-oriented electrical steel sheet according to the present embodiment, a magnetic domain control step of performing a magnetic domain control process may be provided between the cold rolling step and the decarburization annealing step (1 st), between the decarburization annealing step and the annealing separator application step (2 nd), between the smoothing step and the insulating film forming step (3 rd), or after the insulating film forming step (4 th).
By performing the magnetic domain control process, the iron loss of the grain-oriented electrical steel sheet can be further reduced. When the magnetic domain control treatment is performed between the cold rolling step and the decarburization annealing step, between the decarburization annealing step and the annealing separating agent application step, and between the smoothing step and the insulating film formation step, linear or dot-shaped groove portions extending in a direction intersecting the rolling direction are formed at predetermined intervals along the rolling direction, and the width of the 180 ° magnetic domain may be narrowed (180 ° magnetic domain is subdivided).
In the case where the magnetic domain control treatment is performed after the insulating coating forming step, the width of the 180 ° magnetic domain may be narrowed (180 ° magnetic domain is subdivided) by forming linear or spot-like stress strain portions or groove portions extending in the direction intersecting the rolling direction at predetermined intervals along the rolling direction.
In the case of forming the stress strain portion, laser beam irradiation, electron beam irradiation, or the like may be applied. In the case of forming the groove portion, a mechanical groove forming method using a gear or the like, a chemical groove forming method in which a groove is formed by electrolytic etching, a thermal groove forming method using laser irradiation, or the like can be applied. When the insulating film is damaged by formation of the stress-strained portion or the groove portion and the characteristics such as insulation properties are deteriorated, the insulating film may be formed again to repair the damage.
Fig. 1 shows an example of a method for producing a grain-oriented electrical steel sheet according to the present embodiment. The work surrounded by the solid line is indicated as an essential process, and the work surrounded by the broken line is indicated as an optional process.
The grain-oriented electrical steel sheet produced by the production method of the present embodiment does not have a forsterite coating. Specifically, the grain-oriented electrical steel sheet includes a mother steel sheet, an intermediate layer disposed in contact with the mother steel sheet, and an insulating coating disposed in contact with the intermediate layer and serving as an outermost surface.
The grain-oriented electrical steel sheet may not have a forsterite coating film as long as it is confirmed by X-ray diffraction. For example, the surface of the grain-oriented electrical steel sheet from which the insulating coating has been removed may be subjected to X-ray Diffraction, and the obtained X-ray Diffraction spectrum may be compared with PDF (Powder Diffraction File). For example, for forsterite (Mg)2SiO4) So long as the JCPDS numbering is used: 34-189. In the present embodiment, when the main component of the X-ray diffraction spectrum is not forsterite, it is determined that the grain-oriented electrical steel sheet does not have a forsterite coating.
In order to remove only the insulating coating from the grain-oriented electrical steel sheet, the grain-oriented electrical steel sheet having the coating may be immersed in a high-temperature alkaline solution. Specifically, the reaction is carried out by reacting NaOH: 30 mass% + H2O: immersing in 70% by mass aqueous solution of sodium hydroxide at 80 ℃ for 20 minutes, washing with water and dryingThe insulating coating can be removed from the grain-oriented electrical steel sheet by drying. Generally, only the insulating coating is dissolved by an alkaline solution, and the forsterite coating is dissolved by an acidic solution such as hydrochloric acid.
The grain-oriented electrical steel sheet produced by the production method of the present embodiment has excellent magnetic properties (iron loss properties) because it does not have a forsterite coating, and also has excellent coating adhesion because each production process is optimally controlled.
Example 1
Next, examples of the present invention will be described, but the conditions in the examples are one example of conditions adopted for confirming the feasibility and the effects of the present invention, and the present invention is not limited to the one example of conditions. As long as the object of the present invention is achieved without departing from the gist of the present invention, various conditions can be adopted in the present invention.
In the steel slabs of the chemical compositions shown in Table 1, No. A13 and No. a11 were heated to 1350 ℃ and subjected to hot rolling to obtain hot-rolled steel sheets having a thickness of 2.6 mm. The hot-rolled steel sheet was subjected to one cold rolling or multiple cold rolling with intermediate annealing interposed therebetween to obtain a cold-rolled steel sheet having a final thickness of 0.22 mm. As the decarburization annealing step, the cold rolled steel sheet having a thickness of 0.22mm was subjected to decarburization annealing under the conditions shown in tables 2 to 4.
In addition, in the steel slabs of the chemical compositions shown in Table 1, the steel slabs were heated to 1150 ℃ in addition to No. A13 and No. a11 and subjected to hot rolling to obtain hot-rolled steel sheets having a thickness of 2.6 mm. The hot-rolled steel sheet was subjected to cold rolling once or multiple times with intermediate annealing interposed therebetween to obtain a cold-rolled steel sheet having a final thickness of 0.22 mm. As a decarburization annealing step, a cold rolled steel sheet having a thickness of 0.22mm was subjected to decarburization annealing under the conditions shown in tables 2 to 4, and a nitriding treatment was performed by holding the steel sheet in an ammonia-containing atmosphere during the temperature reduction.
In the case of No. b5, the hot-rolled steel sheet after hot rolling was subjected to hot-rolled sheet annealing in which annealing was performed at 1100 ℃ and then annealing was performed at 900 ℃, and then, the steel sheet was pickled to remove scale formed on the surface and then cold-rolled.
In the decarburization annealing, the average heating rate in the temperature raising process to the annealing temperature is lower than 15 ℃/sec.
Al is applied to the decarburized and annealed sheet after the decarburization annealing2O3Ratio to MgO (MgO/(Al)2O3+ MgO)) and a hydration moisture are annealing separators under the conditions shown in tables 2 to 4 and dried.
For the decarburization annealed sheet coated with the annealing separator, final annealing was performed at 1100 ℃ or 1200 ℃. The final annealing conditions were set as described in tables 5 to 7.
After the final annealing, as shown in tables 5 to 7, the remaining annealing separator was removed from the surface of the final annealed sheet by water washing and acid washing. The water washing is performed using a solution to which an inhibitor, i.e., at least 1 of triethanolamine, rosin amine, or thiol, is added. The acid washing was performed with an aqueous sulfuric acid solution (sulfuric acid concentration by volume: 1 vol%). In comparative examples nos. b15 to b17, acid washing was not performed.
After removing the remaining annealing separator from the final annealed sheet, the final annealed sheet was subjected to smoothing annealing under the mixed gas atmosphere conditions and annealing temperature conditions shown in tables 8 to 10. By this smoothing annealing, the surface of the final annealed sheet is smoothed.
Thereafter, an insulating film was formed by applying a coating liquid of an insulating film containing colloidal silica and phosphate as main components and, if necessary, anhydrous chromic acid, sintering the coating liquid at the sintering temperatures shown in tables 8 to 10, and further performing heat treatment at the temperatures shown in tables 8 to 10.
In each example, as shown in tables 11 to 13, the magnetic domain control treatment was performed at any time between the cold rolling step and the decarburization annealing step (1 st), between the decarburization annealing step and the annealing separating agent application step (2 nd), between the smoothing step and the insulating film forming step (3 rd), or after the insulating film forming step (4 th). In the magnetic domain control treatment, grooves are formed either mechanically or chemically, or stress strain portions or groove portions are formed using a laser.
The obtained grain-oriented electrical steel sheets No. B1 to B46 and B1 to B33 were evaluated for iron loss and film adhesion.
< iron loss >
The samples collected from the grain-oriented electrical steel sheets thus produced were measured in accordance with JIS C2550-1: 2000, the iron loss W17/50(W/kg) at an excitation magnetic flux density of 1.7T and a frequency of 50Hz was measured by the Epstein test. In the grain-oriented electrical steel sheet subjected to the magnetic domain control, it was judged as acceptable when the iron loss W17/50 was less than 0.7W/kg. In addition, the grain-oriented electrical steel sheet having no magnetic domain control had an iron loss W17/50 of less than 1.0W/kg, and was judged as acceptable.
< film adhesion >
Test pieces obtained from the produced grain-oriented electrical steel sheets were wound around a cylinder having a diameter of 20mm (180 ° bend), and the coating adhesion of the insulating coating was evaluated as the percentage of the remaining area of the coating at the time of unwinding. Evaluation of film adhesion of the insulating film the presence or absence of peeling of the insulating film was determined by visual observation. The non-peeling property from the steel sheet and the coating residual area ratio of 90% or more was-. A case where the residual area ratio of the coating film was 85% or more (excellent or good as described above) was judged as good.
The results are shown in tables 11 to 13.
TABLE 1
Figure BDA0003157671890000231
TABLE 2
Figure BDA0003157671890000241
TABLE 3
Figure BDA0003157671890000251
TABLE 4
Figure BDA0003157671890000261
TABLE 5
Figure BDA0003157671890000271
In addition, the method is as follows: hydrogen-nitrogen mixed atmosphere gas (described in terms of hydrogen ratio)
In addition, 2: amount of iron-based hydroxide and amount of iron-based oxide (per side)
TABLE 6
Figure BDA0003157671890000281
The original color 1 is hydrogen-nitrogen mixed atmosphere gas (recorded in hydrogen ratio)
Orange 2 iron based hydroxide and iron based oxide (per single side)
TABLE 7
Figure BDA0003157671890000291
In addition, the method is as follows: hydrogen-nitrogen mixed atmosphere gas (described in terms of hydrogen ratio)
In addition, 2: amount of iron-based hydroxide and amount of iron-based oxide (per side)
TABLE 8
Figure BDA0003157671890000301
TABLE 9
Figure BDA0003157671890000311
Watch 10
Figure BDA0003157671890000321
TABLE 11
Figure BDA0003157671890000331
TABLE 12
Figure BDA0003157671890000341
Watch 13
Figure BDA0003157671890000351
As can be seen from tables 1 to 13, all the process conditions of nos. B1 to B46 as inventive examples satisfy the scope of the present invention, and the iron loss is low. In addition, the coating film also has excellent adhesion.
In contrast, in comparative examples nos. b1 to b33, 1 or more process conditions were out of the range of the present invention, and the iron loss and/or the film adhesion were poor. In comparative example No. b25, since rolling was impossible, the following evaluation was not performed.
Industrial applicability
According to the aspect of the present invention, it is possible to provide a method for producing a grain-oriented electrical steel sheet which does not have a forsterite film and is excellent in magnetic properties and film adhesion. The grain-oriented electrical steel sheet obtained is excellent in magnetic properties and coating adhesion, and therefore the industrial applicability of the present invention is high.

Claims (5)

1. A method for manufacturing a grain-oriented electrical steel sheet, comprising:
a hot rolling step of obtaining a hot-rolled steel sheet by hot-rolling a steel slab having a chemical composition comprising, in mass%:
C：0.030～0.100％、
Si：0.80～7.00％、
Mn：0.01～1.00％、
total of S and Se: 0 to 0.060%,
Acid-soluble Al: 0.010-0.065%,
N：0.004～0.012％、
Cr：0～0.30％、
Cu：0～0.40％、
P：0～0.50％、
Sn：0～0.30％、
Sb：0～0.30％、
Ni：0～1.00％、
B：0～0.008％、
V：0～0.15％、
Nb：0～0.20％、
Mo：0～0.10％、
Ti：0～0.015％、
Bi：0～0.010％，
The remainder comprising Fe and impurities;
a cold rolling step of cold rolling the hot-rolled steel sheet to obtain a cold-rolled steel sheet;
a decarburization annealing step of performing decarburization annealing on the cold-rolled steel sheet to obtain a decarburization annealed sheet;
coating Al-containing on the decarburized annealed sheet2O3An annealing separating agent coating step of drying the annealing separating agent and MgO;
a final annealing step of performing final annealing on the decarburized annealed sheet coated with the annealing separator to obtain a final annealed sheet;
an annealing separating agent removing step of removing the remaining annealing separating agent from the surface of the final annealed sheet;
a smoothing step of smoothing the surface of the final annealed sheet from which the residual annealing separator is removed; and
an insulating coating forming step of forming an insulating coating on the surface of the final annealed plate after the smoothing step,
in the decarburization annealing step, the decarburization annealing step is performed,
at the oxidation degree, i.e. pH2O/PH2Is maintained at an annealing temperature of 750 to 900 ℃ for 10 to 600 seconds in an atmosphere of 0.18 to 0.80,
in the step of applying the annealing separator,
the MgO and the Al in the annealing separating agent are mixed2O3At a mass ratio of MgO/(MgO + Al)2O3) 5 to 50% and a hydration water content of 1.5 mass% or less,
in the final annealing process, the annealing temperature is controlled,
maintaining the decarburized and annealed sheet coated with the annealing separator at a temperature of 1100 to 1200 ℃ for 10 hours or more in a mixed gas atmosphere containing 50% or more of hydrogen in terms of volume ratio,
in the annealing separator removing step, the annealing separator is removed,
after the final annealed plate is washed with water using a solution to which at least 1 of triethanolamine, rosin amine, or thiol, i.e., an inhibitor, is added,
pickling the final annealed sheet with an acidic solution having a concentration of less than 20% by volume, thereby controlling the amount of iron-based hydroxide and iron-based oxide on the surface of the final annealed sheet to 0.9g/m per surface2In the following, the following description is given,
in the smoothing step, the smoothing step is performed,
annealing the final annealed sheet from which the remaining annealing separator has been removed at a temperature of 1000 ℃ or higher in a mixed gas atmosphere containing 50% or more of hydrogen or carbon monoxide by volume,
in the step of forming the insulating coating film,
and coating a coating liquid of an insulating coating film containing phosphate or colloidal silica as a main component on the surface of the final annealed plate after the final annealing, sintering at 350 to 600 ℃, and performing heat treatment at 800 to 1000 ℃ to form the insulating coating film.
2. The method of manufacturing a grain-oriented electrical steel sheet according to claim 1, further comprising at least 1 of a hot-rolled sheet annealing step of annealing the hot-rolled steel sheet and a hot-rolled sheet pickling step of pickling between the hot-rolling step and the cold-rolling step.
3. The method of manufacturing a grain-oriented electrical steel sheet according to claim 1 or 2, wherein in the decarburization annealing step, a nitriding treatment is performed in which the cold-rolled steel sheet is annealed in an atmosphere containing ammonia.
4. The method of manufacturing a grain-oriented electrical steel sheet according to any one of claims 1 to 3, further comprising a magnetic domain control step of performing a magnetic domain control process at any time between the cold rolling step and the decarburization annealing step, between the decarburization annealing step and the annealing separator application step, between the smoothing step and the insulating film forming step, or after the insulating film forming step.
5. The method of manufacturing a grain-oriented electrical steel sheet according to any one of claims 1 to 4, wherein the steel slab contains, as a chemical composition, in mass%, a chemical composition selected from the group consisting of:
Cr：0.02～0.30％、
Cu：0.05～0.40％、
P：0.005～0.50％、
Sn：0.02～0.30％、
Sb：0.01～0.30％、
Ni：0.01～1.00％、
B：0.0005～0.008％、
V：0.002～0.15％、
Nb：0.005～0.20％、
Mo：0.005～0.10％、
ti: 0.002 to 0.015% and
Bi：0.001～0.010％、
at least 1 of the group consisting.
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